KR100372569B1 - Flame Retardant Thermoplastic Resin Composition - Google Patents

Abstract

Flame retardant thermoplastic resin composition of the present invention (A) 45-95 parts by weight of polycarbonate resin; (B) (b ₁ ) 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, or mixtures thereof and acrylonitrile, methacrylonitrile, maleic anhydride, C _1-4 alkyl or phenyl N 5-95 parts by weight of a monomer mixture consisting of 50-5% by weight of substituted maleimide or mixtures thereof (b ₂ ) butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, Rubber obtained by graft polymerization on 95-5 parts by weight of a polymer selected from isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), or polyorganosiloxane / polyalkyl (meth) acrylate rubber composites or mixtures thereof 1-50 parts by weight of the modified styrenic graft copolymer; (C) (c ₁ ) 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, or mixtures thereof and (c ₂ ) acrylonitrile, methacrylonitrile, maleic anhydride, C _1-4 0.5-50 parts by weight of a styrenic copolymer composed of 50-5% by weight of alkyl or phenyl N-substituted maleimide, or a mixture thereof; (D) (d ₁ ) C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters, or mixtures thereof 44-90 wt%, (d ₂ ) styrene, α-methylstyrene, halogen or 0.5-50 parts by weight of a copolymer consisting of 5-55% by weight of alkyl substituted styrene, or mixtures thereof, and (d ₃ ) 1-20% by weight of acrylonitrile, methacrylonitrile, or mixtures thereof; (E) 1-30 parts by weight of the phosphate ester compound; And (F) fluorinated polyolefins having an average particle size of 0.05-1000 μm and a density of 1.2-2.3 g / cm ³ based on 100 parts by weight of the components (A) + (B) + (C) + (D). It consists of 0.05-5 parts by weight of resin.

Description

Flame Retardant Thermoplastic Resin Composition

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition comprising a polycarbonate resin, a rubber modified styrene graft copolymer, a styrene copolymer, a (meth) acrylic acid ester copolymer, a phosphate ester flame retardant, and a fluorinated polyolefin resin. .

Background of the Invention

Polycarbonate resins are excellent in transparency, mechanical strength and heat resistance, and are widely used in applications such as electric, electronic products, and automobile parts. However, polycarbonate resins are used in blends with other types of resins in order to improve them since they have disadvantages of poor processability and notched impact strength. For example, the blend of the polycarbonate resin and the rubber-modified styrenic copolymer may be referred to as a resin mixture having improved processability while maintaining high notch impact strength.

Since such polycarbonate-based blend resin compositions are typically applied to large injection moldings such as computer housings or other office equipment, they must maintain high mechanical strength, together with flame retardancy. However, when the blend of the polycarbonate / styrene copolymer stays at a high temperature during the extrusion or injection process, the domain size of the components constituting the dispersed phase is increased, which is a continuous phase (matrix). When the viscosity of the resin forming a lower) it is more easily generated. As the phase size of the components constituting the dispersed phase increases in this way, the mechanical properties of the molding rapidly decrease.

In addition, in order to impart flame retardancy to such a resin composition, a halogen-based flame retardant and an antimony compound have been conventionally used. U.S. Patent Nos. 4,983,658 and 4,883,835 disclose examples of using halogen containing compounds as flame retardants. However, when using a halogen flame retardant, there exists a problem that the gas which arises at the time of combustion is harmful to a human body. Therefore, the demand for resins that do not contain halogen-based flame retardants has recently been expanding rapidly.

As a technique for imparting flame retardancy without using a halogen flame retardant, the most common at present is to use a phosphate ester flame retardant. However, when the amount of the phosphate ester compound flame retardant is increased, not only the heat resistance of the resin composition is lowered, but also the viscosity of the continuous phase resin is lowered, so that a phenomenon of coalescence of the dispersed phase resin is easily generated. The powdered phase of the styrene-based resin having an increased size acts as a fuel source during combustion, which causes a rapid increase in combustion time in evaluating flame retardancy and consequently causes a loss of uniformity in flame retardancy. In addition, the resin composition containing such a low molecular weight phosphate ester flame retardant is known to have a very low bond line strength.

U. S. Patent No. 5,292, 786 discloses a resin composition having improved weld-line strength composed of polycarbonate resin, ABS resin, phosphorus flame retardant and polyalkyl methacrylate resin. However, in the above technique, when the polyalkyl methacrylate resin is used in an appropriate amount or more, the thermal stability and appearance characteristics of the resin composition are degraded due to decomposition (or depolymerization) of the polyalkyl methacrylate resin, and thus, the flame retardant properties of the resin composition are decreased. The problem of degradation occurs.

On the other hand, the present inventors, in order to overcome the above problems, meta (acrylic acid) ester as a compatibilizer in a composition composed of polycarbonate resin, rubber modified styrene graft copolymer, styrene copolymer, phosphate ester flame retardant and fluorinated polyethylene resin By using the copolymer resin, phase aggregation does not occur due to a decrease in the viscosity of the resin at a high temperature, and thus there is no deterioration in the mechanical properties such as non-uniformity of flame retardancy, joint line strength, and impact strength of the molded product at high temperature injection. Therefore, the inventors have developed a flame-retardant thermoplastic resin composition having excellent balance of physical properties such as impact resistance, thermal stability, heat resistance, workability and appearance.

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition in which agglomeration phenomena due to a decrease in viscosity of a resin at high temperature and thus non-uniformity of flame retardancy do not appear.

It is another object of the present invention to provide a thermoplastic resin composition in which mechanical properties such as impact strength of a molded product are not deteriorated during high temperature injection.

Another object of the present invention is to provide a thermoplastic resin composition having excellent weld-line strength.

Still another object of the present invention is to provide a thermoplastic resin composition having excellent balance of physical properties such as impact resistance, thermal stability, heat resistance, workability and appearance.

The above and other objects of the present invention can be achieved by the present invention described below.

The thermoplastic resin composition of the present invention comprises (A) polycarbonate resin, (B) rubber modified styrene graft copolymer, (C) styrene copolymer, (D) (meth) acrylic acid ester copolymer, (E) phosphoric acid It consists of an ester flame retardant and (F) fluorinated polyolefin resin, and the detailed description about each of these components is as follows.

(A) polycarbonate resin

The polycarbonate resin according to the present invention is prepared by reacting diphenols represented by the following formula (1) with phosgene, halogen formate or carbonic acid diester:

Wherein A is a single bond, alkylene of C _1-5 , alkylidene of C _2-5 , cycloalkylidene of C _5-6 , S or SO ₂ .

Examples of the diphenols represented by the above formula include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, and 2,4-bis- (4- Hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2 -Bis- (3,5-dichloro-4-hydroxyphenyl) -propane and the like. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols, such as hydroxyphenyl) -cyclohexane, are preferable, and 2,2-bis- (4-hydroxyphenyl) -propane also called bisphenol-A is the most preferable.

The polycarbonate resin (A) of the present invention has a weight average molecular weight (M _w ) of 10,000 to 200,000, preferably 15,000 to 80,000. A branched polycarbonate resin may be used, and preferably, may be prepared by adding a compound having 0.05-2 mol% of a trivalent or more phenol group to the total amount of diphenols used in the polymerization. The polycarbonate (PC) used in the preparation of the resin composition of the present invention may be used in the form of a homopolymer, a copolymer, or a mixture thereof. In addition, the polycarbonate resin (A) may be used in part or in whole by an aromatic polyester-carbonate resin obtained by polymerizing in the presence of an ester precursor, such as a bifunctional carboxylic acid. The polycarbonate resin (A) is used in the range of 45 to 95 parts by weight.

(B) rubber modified styrene graft copolymer resin

The rubber-modified graft copolymer resin used in the present invention is 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, or mixtures thereof and acrylonitrile, methacrylonitrile, maleic anhydride, C _{1 -4} alkyl or phenyl N-substituted maleimide, or mixtures thereof with 5-50% by weight of mixtures thereof (b ₁ ) 5-95 parts by weight of butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / Butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), and polyorganosiloxane / polyalkyl (meth) acrylate rubber composites selected from the group consisting of (b ₂ ) 5- It is a copolymer grafted to 95 weight part.

Preferred examples of the styrene-based graft copolymers include graft copolymerization of styrene and acrylonitrile monomers in the form of a mixture of butadiene rubber, acrylic rubber, or styrene / butadiene rubber, and acrylonitrile and styrene on butadiene rubber Most preferred is an acrylonitrile / butadiene / styrene (ABS) resin grafted.

The rubber modified styrene graft copolymer is used in the range of 1-50 parts by weight of the total base resin. The average size of the rubber particles used in preparing the graft copolymer is suitably in the range of 0.05 to 4 μm in consideration of impact strength and appearance.

The styrenic graft copolymer resin can be produced by a conventional polymerization method, but it is most suitable to emulsion-polymerize or bulk-polymerize the above-described vinyl monomer in the presence of a rubbery polymer using a polymerization initiator.

(C) Styrene Copolymer Resin

Styrene-based copolymers used in the present invention is 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene or mixtures thereof (c ₁ ) and acrylonitrile, methacrylonitrile, maleic anhydride, C ₁ Styrenic copolymers obtained by copolymerizing 5-50% by weight of _-4 alkyl or phenyl N-substituted maleimide or mixtures thereof (c ₂ ) or mixtures of these copolymers. This styrene copolymer resin is used in 0.5-50 weight part.

The styrenic copolymer may be produced as a by-product in the preparation of the rubber-modified styrenic graft copolymer (B), especially a chain transfer agent used to graf excess monomer to a small amount of rubbery polymer or as a molecular weight regulator. It is more likely to occur when is used excessively. The content of the styrene copolymer (C) used in the preparation of the resin composition of the present invention is not shown including the by-products generated during the production of the rubber-modified styrene-based graft copolymer (B). That is, the styrene-based copolymer (C) used in the production of the resin composition of the present invention is a thermoplastic resin and does not contain a rubbery polymer.

Specific examples of the styrene copolymer (C) include those prepared from a monomer mixture of styrene and acrylonitrile, a monomer mixture of α-methylstyrene and acrylonitrile or a monomer mixture of styrene, α-methylstyrene and acrylonitrile. Can be mentioned. The styrene copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, and it is preferable to use a weight average molecular weight (M _w ) of 15,000-200,000.

Another preferable styrene-based copolymer (C) is a copolymer of styrene and maleic anhydride, which can be produced using a continuous bulk polymerization method and a solution polymerization method. The composition ratio of the two monomer components can be varied in a wide range, preferably, the content of maleic anhydride is 5-25% by weight. A wide range of molecular weights of the styrene / maleic anhydride copolymer may also be used, but it is preferable to use those having a weight average molecular weight of 60,000-200,000 and intrinsic viscosity of 0.3-0.9.

The styrene monomer used in the preparation of the styrenic copolymer (C) of the present invention may be used in place of other substituted styrene based monomers such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and α-methylstyrene. have.

The styrenic copolymers (C) described above can also be used alone or in mixture of two or more thereof.

(D) (meth) acrylic acid ester copolymer

The (meth) acrylic acid ester copolymer (D) used in the resin composition of the present invention is C _1-8 methacrylic acid alkyl ester, C _1-8 acrylic acid alkyl ester or a mixture thereof (d ₁ ) 44-90 wt% , Copolymerization of 5-55% by weight of styrene, α-methylstyrene, halogen, alkyl substituted styrene or mixtures thereof (d ₂ ) and 1-20% by weight of acrylonitrile, methacrylonitrile or mixtures thereof (d ₃ ) It is manufactured by.

The C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters are esters obtained from monohydryl alcohols each containing methacrylic acid or acrylic acid and 1-8 carbon atoms. As a preferable specific example, methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, or methacrylic acid propyl ester is mentioned, Among these, methacrylic acid methyl ester is the most preferable.

The (meth) acrylic acid ester copolymer (D) is used as a compatibilizer in the resin composition of the present invention, and is a polycarbonate resin (A), a rubber-modified styrene graft copolymer (B) and a styrene copolymer Excellent compatibility with each of (C) improves the compatibility of the thermoplastic resin composition of the present invention.

As the method for producing the (meth) acrylic acid ester copolymer (D), any of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used, and a weight average molecular weight of 20,000-300,000 may be used. It is preferable.

The (meth) acrylic acid ester copolymer (D) used in the preparation of the resin composition of the present invention is added in the range of 0.5-50 parts by weight, and preferably used in the range of 1-40 parts by weight.

(E) Phosphoric Acid Ester Compound

The phosphate ester flame retardant used in the preparation of the resin composition of the present invention may be used alone or in combination with the following (e ₁ ), (e ₂ ), (e ₃ ).

(e ₁ ) phosphate ester compound

As a phosphate ester compound or a mixture of phosphate ester compounds represented by the following formula (2), Japanese Patent Publication No. 59-202,240 discloses a method for producing such a compound.

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each C _6-20 aryl or alkyl substituted C _6-20 aryl groups, and R ₃ is C _6-30 aryl or alkyl substituted C _6-30 aryl groups Derivatives. Preferred R ₁ , R ₂ , R ₄ and R ₅ are phenyl groups or phenyl groups substituted with alkyl groups such as methyl, ethyl, isopropyl, t-butyl, isobutyl, isoamyl, t-amyl, double phenyl or methyl, Most preferred are phenyl groups substituted with ethyl, isopropyl or t-butyl groups. As R ₃ , resorcinol, hydroquinone or bisphenol-A is preferable. The l represents the number average degree of polymerization, the average value of l is from 0 to 3.

The phosphate ester compound is preferably an oligomeric phosphate ester compound derived from an alkyl substituted C _6-30 aryl group having an average value of 0-3. In the present invention, a phosphate ester compound having a value of l of 0, 1, 2, and 3 may be used alone or in a mixed form, each of which is already mixed or prepared separately in the polymerization process. It is also preferable to use a mixture of phosphate ester compounds having different l values.

Among the phosphate esters used in the present invention, phosphate esters having an l value of 0 include one or two of tri (alkylphenyl) phosphate, di (alkylphenyl) monophenylphosphate, diphenylmono (alkylphenyl) phosphate or triphenylphosphate. It is preferable to use the above mixture.

(e ₂ ) Phosphate ester morphide compound

It is prepared by reacting an aromatic alcohol with morpholine to phosphorus oxychloride (POCl ₃ ) as a phosphate ester morphide compound represented by the following formula (3) or a mixture thereof.

Wherein x is 1, 2, or 3, and R ₆ represents a C _6-20 aryl or alkyl substituted C _6-20 aryl group. Preferred examples of R ₆ include phenyl group, cresyl group, t-butylphenyl group, isopropylphenyl group and the like. Of these, x is 1 or 2, and R ₆ is most preferably a phenyl group or a cresyl group.

The method for producing the phosphate ester morphide compound is not particularly limited, and is usually obtained by reacting an aromatic alcohol and morpholine with phosphorus oxychloride (POCl ₃ ). The composite may contain about 0-20% by weight of triaryl phosphate depending on the reaction process, and may be used as it is or purified. In the case of a mixture, 1-99% by weight of the compound having x = 1, 1-99% by weight of the compound having x = 2, and 0-20% by weight of the compound having x = 3 based on the flame retardant 100.

(e ₃ ) Oligomeric Phosphate Ester Morphoxide Compound

As an oligomeric phosphate ester morphide-based compound represented by the following formula (4) or a mixture thereof, hydroxy aryl compounds such as resorcinol, hydroquinone, bisphenol-A and arylmorpholino chlorophosphate are conventionally used by using an appropriate catalyst. Prepared by the method.

Wherein y is 1 or 2, R ₇ is C _6-20 aryl or alkyl substituted C _6-20 aryl group, R ₈ is C _6-30 aryl or alkyl substituted C _6-30 aryl group derivative. In the above formula, n and m each represent a number average degree of polymerization, and an average value of n + m is 0-3.

Preferred examples of R ₇ are a phenyl group or a phenyl group substituted with an alkyl group such as methyl, ethyl, isopropyl, t-butyl, isobutyl, isoamyl, t-amyl, a double phenyl group or methyl, ethyl, isopropyl or t- Most preferred is a phenyl group substituted with a butyl group. R ₈ is preferably resorcinol, hydroquinone or bisphenol-A.

That is, the flame retardant component (E ₃ ) used in the preparation of the resin composition of the present invention is an aryl derivative oligomeric phosphate ester morphide compound having an average value of n + m of 0-3. In the present invention, phosphate ester morpholide compounds having n + m values of 0, 1, 2, and 3 may be used alone or in a mixed form, each of which is already mixed when it is prepared in the polymerization process. Alternatively, it is also preferable to use a mixture of phosphate ester morphide compounds having different n + m values prepared separately.

The method for preparing the oligomeric phosphate ester morpholide suitable for the present invention is not particularly limited, and the hydroxy aryl compounds such as resorcinol, hydroquinone and bisphenol-A and arylmorpholino chlorophosphate are usually used by using an appropriate catalyst. Can be prepared by reaction. In this case, arylmorpholino chlorophosphate may be prepared by reacting phosphorus oxychloride (POCl ₃ ) with an aromatic alcohol and morpholine. According to the reaction process, diaryl chlorophosphate and dimorpholino chlorophosphate may be 0-20% by weight. May be included.

The oligomeric phosphate ester morphide prepared in the above manner is 0-10% by weight of 0 and n + m, and 50-100% by weight of n + m is 1 depending on the reaction process. 0-40 weight% of the value of + m is 2 or more is contained. The prepared composite can be used as it is or as a refined flame retardant, even when a mixture of a number of compounds does not change the properties as a flame retardant.

(F) fluorinated polyolefin resin

The fluorinated polyolefin resin (F) used in the preparation of the flame retardant thermoplastic resin composition of the present invention may be prepared using a known polymerization method, for example, a pressure of 7-71 kg / cm ² and a temperature of 0-200 ° C. , Preferably at 20-100 ° C., in an aqueous medium containing free radical forming catalysts such as sodium, potassium or ammonium peroxydisulfate.

Preferred specific examples of the fluorinated polyolefin resin (F) include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer And ethylene / tetrafluoroethylene copolymers, and the like, polytetrafluoroethylene having a particle size of 0.05-1,000 μm and specific gravity of 1.2-2.3 g / cm ³ is most preferred. These may be used independently from each other, and two or more different types may be used together.

When the fluorinated polyolefin resin is mixed with other component resins of the present invention and extruded, a fluorinated polyolefin-based resin forms a fibrillar network in the resin, thereby lowering the flow viscosity of the resin during combustion and increasing the shrinkage rate, thereby dropping the resin. It is to prevent the phenomenon.

The fluorinated polyolefin resin may be used in an emulsion state or a powder state. When the fluorinated polyolefin resin in an emulsion state is used, the dispersibility in the entire resin composition is good, but the manufacturing process is complicated. Therefore, even if it is powder state, if it can disperse | distribute suitably in the whole resin composition and can form a fibrous network, it is preferable to use it in powder state.

The content of the fluorinated polyolefin resin used in the production of the resin composition of the present invention is 0.05-5 parts by weight based on 100 parts by weight of (A) + (B) + (C) + (D).

The flame retardant thermoplastic resin composition of the present invention may include, in addition to the above components, general additives such as flame retardant aids, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, inorganic additive pigments or dyes, and the like according to their respective uses. The inorganic additive to be used may be used in the range of 0-60 parts by weight, preferably 1-40 parts by weight, based on 100 parts by weight of (A) + (B) + (C).

The resin composition of the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.

The composition of the present invention can be used for molding a variety of products, and is particularly suitable for the manufacture of housings of electrical and electronic products, such as computer housings that require flame retardancy, bond strength and high impact resistance while being injected at high temperatures.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

(A) polycarbonate resin, (B) rubber modified styrene graft copolymer resin, (C) styrene copolymer resin, (D) (meth) acrylic acid ester-based air used in the following Examples and Comparative Examples Specifications of the copolymer, (E) phosphate ester flame retardant, and (F) fluorinated polyolefin resin are as follows.

(A) polycarbonate resin

A polycarbonate of bisphenol-A type having a weight average molecular weight (Mw) of 25,000 was used.

(B) rubber modified styrene graft copolymer resin

Butadiene rubber latex was added so that the butadiene content was 45 parts by weight based on the total amount of the monomers, 1.0 parts by weight of potassium oleate, cumene hydroperoxide, an additive necessary for a mixture of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water. 0.4 parts by weight, 0.3 parts by weight of mercaptan-based chain transfer agent was added to the reaction while maintaining at 75 ℃ for 5 hours to prepare an ABS graft latex. A 1% sulfuric acid solution was added to the resulting polymer latex, coagulated and dried to use the graft copolymer resin as a powder.

(C) Styrene Copolymer Resin

Suspended by adding 71 parts by weight of styrene, 29 parts by weight of acrylonitrile and 120 parts by weight of deionized water, 0.2 part by weight of azobisisobutyronitrile, 0.3 part by weight of mercaptan-based chain transfer agent and 0.5 part by weight of tricalcium phosphate The polymerization was performed to prepare a SAN copolymer resin. The copolymer was washed with water, dehydrated and dried to use a powdery SAN copolymer resin.

(D) (meth) acrylic acid ester copolymer

0.2 part by weight of azobisisobutyronitrile, a polymerization initiator, 0.3 part by weight of mercaptan-based chain transfer agent, in a mixture of 70 parts by weight of methacrylic acid methyl ester, 20 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 120 parts by weight of deionized water; The suspension was polymerized by adding 0.5 parts by weight of tricalcium phosphate to prepare a copolymer resin. The (meth) acrylic acid ester copolymer was washed with water, dehydrated and dried to form a powder.

(E) Phosphate Ester Flame Retardant

(e _1a ) In Formula 2, l = 0 is 3.4 wt%, l = 1 is 85.4 wt%, and the value of l is included in 11.1 wt%, and the average l = 1.0, R ₁ , R ₂ , Bisphenol-A derived oligomeric phosphate esters in which R ₄ and R ₅ are each a phenyl group were used.

(e _1b ) Triphenylphosphate having l = 0 in Chemical Formula 2 was used.

(e ₂ ) Phosphorus oxychloride was obtained by reacting phenol and morpholine, and this compound contained 9% by weight of triphenylphosphate, and R ₆ is a phenyl group in Formula 3, and 86% by weight of a compound having x 1 A mixture of a phosphate ester morpholide compound containing 5% by weight of a compound in which R ₆ is a phenyl group and x is 2 was used.

(e ₃ ) The oligomeric phosphate ester morphide compound was reacted with resorcinol and phenylmorphorino chlorophosphate. In Formula 4, R ₇ is a phenyl group and R ₈ is a resorcinol derivative. At this time, 1.5% by weight of a phosphate ester morpholide compound having n and m of 0 and y of 1, 68.4% by weight of a compound of which y is 1 and the value of n + m is 1, and y is 1 and the value of n + m A mixture of oligomeric phosphate ester morpholide compounds containing 30.1% by weight of these two or more compounds was used.

(F) fluorinated polyolefin resin

Teflon (trade name) 7AJ of Dupont, USA was used.

Example 1-5

Each component of the composition shown in Table 1, antioxidant and heat stabilizer were added, mixed in a conventional mixer, extruded at a temperature of 240 ° C. using a twin screw extruder having L / D = 35 and Φ = 45 mm, and then extruded. Water was prepared in pellet form.

Comparative Example 1-4

In Comparative Examples 1 and 3, polymethymethacrylate resin (IH-830 of LG Chem, Korea) was used as a compatibilizer, except that the composition of each component was changed as described in Table 1-4. The specimen was prepared in the same manner.

ingredient Example Comparative Example One 2 3 4 5 One 2 3 4 (A) Polycarbonate resin 73 80 80 70 70 73 80 80 70 (B) Styrene Copolymer Resin 10 10 10 10 10 10 10 10 10 (C) Styrene Copolymer 7 5 5 7 10 7 10 - 20 (D) (meth) acrylic acid ester copolymer 10 5 5 13 10 - - - - (D ') polymethyl methacrylate - - - - - 10 - 10 - (E) Phosphate Ester Compound (e _1a ) Bisphenol-A derived oligomeric phosphate ester 10 - - 10 - 10 - - - (e _1b ) triphenylphosphate 2 - - - - 2 - 12 - (e ₂ ) phosphate ester morpholide compound - 12 2 2 - - 12 - - (e ₃ ) oligomeric phosphoric acid ester morpholide compound - - 10 - 12 - - - 12 (F) Fluorinated polyolefin resin 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

(1) Thermal stability measurement

The thermal stability of the resin composition prepared by the above method was measured by reducing the mass of the composition while increasing the temperature at a rate of 20 ° C./min in a nitrogen atmosphere to measure the decomposition start temperature. At this time, the temperature at which the resin actually decomposed after the temperature at which the flame retardant was volatilized was measured.

(2) Measurement of seam strength and general physical properties

Specimens were prepared using a 10 oz injection machine at normal injection conditions at an injection temperature of 250 ° C. to measure seam strength and general physical properties. After leaving the specimens at 23 ° C. and 50% relative humidity for 40 hours, the physical properties were measured according to ASTM D256.

(3) Measurement of physical properties at high temperature injection

In order to measure the properties of high-temperature injection, specimens were prepared using a 10 oz injection machine with a cooling time of 5 minutes at an injection temperature of 280 ° C. It was.

(4) flame retardancy evaluation

Specimens for flame retardancy evaluation were prepared at 250 ° C. using a 10 oz injection machine. Flame retardancy was evaluated according to the UL-94VB evaluation standard defined by the Underwriters Laboratory, and the combustion time and the average combustion time when two flames were applied to five specimens were measured.

(5) heat resistance measurement

Heat resistance was evaluated by ASTM D1525.

Table 2 shows the physical properties of the resins prepared in Examples 1-5 and Comparative Examples 1-4. Example 1-5 is a case of using a compatibilizer (methacrylic acid ester copolymer) according to the present invention, Comparative Examples 1, 3 is a polymethyl methacrylate as a compatibilizer, Comparative Examples 2, 4 Is when no compatibilizer is used.

Properties Example Comparative Example One 2 3 4 5 One 2 3 4 UL94 flame retardant (1/12 ″) V-0 V-0 V-0 V-0 V-0 V-1 V-0 V-2 V-2 Average burning time (seconds) 2.0 2.2 2.1 1.9 2.7 3.2 3.5 4.6 8.5 Maximum single burning time (sec) 4 5 5 4 6 11 9 12 15 Dropping water 0/5 0/5 0/5 0/5 0/5 0/5 0/5 2/5 2/5 Hot Injection Notch Impact Strength (1/8 ″, kgcm / cm) 33 35 33 30 31 28 12 27 11 Bond line impact strength (1/8 ", kgcm / cm) 14 15 15 13 13 13 10 13 9 Heat resistance temperature (VST, ℃) 91 90 94 90 90 91 91 90 91 Decomposition start temperature (℃) 405 411 412 401 406 383 416 385 415

From the results in Table 2, when the compatibilizer is used, the V-0 flame retardant grade can be obtained when the polycarbonate resin content is high (80 parts by weight) or low (70 parts by weight), but the compatibilizer is not used. Otherwise, if the polycarbonate resin content is low (70 parts by weight), the V-0 flame retardant grade cannot be obtained, and even if the polycarbonate resin content is high (80 parts by weight), the flame retardant grade may be represented as V-0. Due to the nonuniformity of the combustion time, a single combustion time was found to be large.

In addition, when the compatibilizer according to the present invention is used, the bond line impact strength and the high-temperature injection notch impact strength (1/8 ″, kg · cm / cm) are superior to those without the compatibilizer and thermal stability is not deteriorated. It was found that.

On the other hand, when polymethyl methacrylate was used as the compatibilizer as shown in Comparative Examples 1 and 3, the joint strength and the impact strength of the high-temperature injection specimens were relatively good, but the thermal stability of the resin was very low. Also in this case, due to the nonuniformity of the combustion time, it can be seen that a single combustion time is large.

According to the present invention, by using a (meth) acrylic acid ester copolymer as a compatibilizer, there is no appearance of agglomeration due to a decrease in viscosity of the resin at high temperatures and non-uniformity of flame retardancy. It does not show any deterioration in physical properties, and has excellent balance of properties such as weld-line strength, impact resistance, thermal stability, heat resistance, workability and appearance, thereby producing an injection molding of a computer housing or other office equipment. It has the effect of providing a flame retardant thermoplastic resin composition useful for.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (10)

(A) 45-95 parts by weight of polycarbonate resin; (B) (b ₁ ) 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, or mixtures thereof and acrylonitrile, methacrylonitrile, maleic anhydride, C _1-4 alkyl or phenyl N 5-95 parts by weight of a monomer mixture consisting of 50-5% by weight of substituted maleimide or mixtures thereof (b ₂ ) butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, Rubber obtained by graft polymerization on 95-5 parts by weight of a polymer selected from isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), or polyorganosiloxane / polyalkyl (meth) acrylate rubber composites or mixtures thereof 1-50 parts by weight of the modified styrenic graft copolymer; (C) (c ₁ ) 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, or mixtures thereof and (c ₂ ) acrylonitrile, methacrylonitrile, maleic anhydride, C _1-4 0.5-50 parts by weight of a styrenic copolymer composed of 50-5% by weight of alkyl or phenyl N-substituted maleimide, or a mixture thereof; (D) (d ₁ ) C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters, or mixtures thereof 44-90 wt%, (d ₂ ) styrene, α-methylstyrene, halogen or 0.5-50 parts by weight of a copolymer consisting of 5-55% by weight of alkyl substituted styrene, or mixtures thereof, and (d ₃ ) 1-20% by weight of acrylonitrile, methacrylonitrile, or mixtures thereof; (E) 1-30 parts by weight of the phosphate ester compound; And (F) Fluorinated polyolefin resin having an average particle size of 0.05-1000 μm and a density of 1.2-2.3 g / cm ³ with respect to 100 parts by weight of the components (A) + (B) + (C) + (D). 0.05-5 parts by weight; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The method of claim 1, wherein the C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters (d ₁ ) are methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester and methacrylic acid Flame retardant thermoplastic resin composition, characterized in that selected from the group consisting of propyl esters. The flame retardant thermoplastic resin composition according to claim 1, wherein the phosphate ester compound (E) is (e ₁ ), (e ₂ ), (e ₃ ), or a mixture thereof. (e ₁ ) A phosphate ester compound represented by the following formula (2) or a mixture thereof: Formula (2) In formula (2), R ₁ , R ₂ , R ₄ and R ₅ are each C _6-20 aryl or alkyl substituted C _6-20 aryl group, and R ₃ is C _6-30 aryl or alkyl substituted C _{A 6-30} aryl group derivative, l is a number average degree of polymerization, and the average value of l is 0-3; (e ₂ ) Phosphate ester morphide compound represented by the following general formula (3) or a mixture thereof: Formula (3) In formula (3), x is 1, 2 or 3, and R ₆ is a C _6-20 aryl or alkyl substituted C _6-20 aryl group; And (e ₃ ) Oligomeric phosphate ester morphide compound or a mixture thereof represented by the following general formula (4): Formula (4) In formula (4), y is 1 or 2, R ₇ is C _6-20 aryl or alkyl substituted C _6-20 aryl group, R ₈ is C _6-30 aryl or alkyl substituted C _6-30 Aryl group derivative, n and m are each number average degree of polymerization, and the average value of n + m is 0-3. delete delete delete delete delete delete The molded article manufactured from the resin composition of any one of said Claims 1-3.